Agents for influencing plant growth

Abstract

Agents for influencing plant growth, containing as active ingredient an azolylacetophenone oxime ether of the formula ##STR1## where R and R¹ independently of one another are each hydrogen, halogen, alkyl, cycloakyl, alkoxy, alkylthio, alkylsulfonyl, haloalkyl, nitro, cyano, phenyl or phenoxy, R² is hydrogen, alkyl, aralkyl, allyl or propargyl, R³ is a divalent radical of the formula --(CH₂)_m --, --(CH₂ CH₂ O--)_u CH₂ CH₂ --, --(CH₂)_v CH═CH--(CH₂)_t -- or --(CH₂)_v --C.tbd.C--(CH₂)_t --, n, p, u, v and t independently of one another are each 1, 2 or 3, m is an integer from 2 to 10, and Az is 1,2,4-triazol-1-yl, pyrazol-1-yl or imidazol-1-yl, or a salt or metal complex thereof, and a method of influencing plant growth or of destroying unwanted plants with these active ingredients.

Description

The present invention relates to agents which are based on azolylacetophenone oxime ethers and which influence the growth of plants or act as herbicides.

It has been disclosed that azolylacetophenone oxime ethers can be used as fungicides (German Laid-Open Application No. DOS 2,431,407). Bioregulator, plant growth regulator or herbicidal activity of such oxime ethers is unknown to date.

We have found that azolylacetophenone oxime ethers of the formula (I) ##STR2## where R and R¹ independently of one another are each hydrogen, halogen, alkyl, cycloalkyl, alkoxy, alkylthio, alkylsulfonyl, haloalkyl, nitro, cyano, unsubstituted or substituted phenyl or unsubstituted or substituted phenoxy, R² is hydrogen, alkyl, aralkyl or unsubstituted or substituted allyl or is propargyl, R³ is a divalent radical of the formula --(CH₂)_m --, --(CH₂ CH₂ O--)_u CH₂ CH₂ --, --(CH₂)_v --CH═CH--(CH₂)_t -- or --(CH₂)_v --C.tbd.C--(CH₂)_t --, n, p, u, v and t independently of one another are each 1, 2 or 3, m is an integer from 2 to 10, and Az is 1,2,4-triazol-1-yl, pyrazol-1-yl or imidazol-1-yl, and their salts and metal complexes can be used successfully as bioregulators, i.e. agents for influencing plant growth, in the widest sense.

The action can extend to modification of the form of growth of the plants, alteration of substances present in the plants, and destruction of undesirable plants.

In formula (I), R and R¹ independently of one another are each, for example, halogen (fluorine, chlorine or bromine), nitro, cyano, alkyl or alkylsulfonyl, each of 1 to 4 carbon atoms, alkoxy or alkylthio, each of 1 or 2 carbon atoms, haloalkyl of 1 to 4, in particular 1 or 2, carbon atoms, and 1 to 5 halogen atoms, in particular 1 to 3 identical or different halogen atoms, preferred halogen atoms being fluorine and chlorine. Haloalkyl is particularly preferably trifluoromethyl.

R and R¹ independently of one another can furthermore be phenoxy or phenyl which is unsubstituted or, preferably, monosubstituted or polysubstituted (disubstituted or trisubstituted) by identical or different substituents, preferred substituents in each case being halogen, in particular fluorine, chlorine or bromine, cyano, nitro and haloalkyl of 1 or 2 carbon atoms and not more than 3 identical or different halogen atoms, preferred halogen atoms being fluorine and chlorine, and an example of haloalkyl being trifluoromethyl.

In formula (I), R² is preferably straight-chain or branched alkyl of 1 to 5 carbon atoms, e.g. methyl, ethyl, n-propyl, isopropyl, sec.-butyl or neopentyl. R² may furthermore be aralkyl where alkyl is of 1 to 4 carbon atoms, unsubstituted phenyl being the preferred aryl. Examples of aralkyl are thus benzyl, phenethyl, phenylpropyl and phenylbutyl. R² can also be allyl which is unsubstituted or substituted by 1, 2 or 3 chlorine atoms, or can be propargyl. Examples of allyl radicals are allyl, 2,3-dichloroallyl and 2,3,3-trichloroallyl.

In formula (I), R³ is a divalent radical of the formula --(CH₂)_m --, for example --CH₂ CH₂ --, --(CH₂)₃ --, --(CH₂)₄ --, --(CH₂)₅ --, (CH₂)₆ --, (CH₂)₇ -- or --(CH₂)₈ --.

R³ can furthermore be a divalent radical containing one, two or three oxygen atoms, of the formula --(CH₂ CH₂ O)_u CH₂ CH₂ --, for example --CH₂ CH₂ OCH₂ CH₂ --, --CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ -- or --(CH₂ CH₂ O)₃ CH₂ CH₂ --.

Finally, R³ can be a divalent radical which contains a double or triple bond and is of the formula --(CH₂)_v --CH═CH--(CH₂)_t or --(CH₂)_v --C.tbd.C--(CH₂)_t --.

Examples are --CH₂ --CH═CH--CH₂ --, --(CH₂)₂ --CH═CH--(CH₂)₂ --, --(CH₂)₃ --CH═CH--(CH₂)₃ --, --CH₂ --CH═CH--CH₂ --, --(CH₂)₂ --C.tbd.C--(CH₂)₂ -- and --(CH₂)₃ --C═C--(CH₂)₃ --.

m is an integer from 2 to 10, preferably from 2 to 8.

If the agents are intended for use as growth regulators in the narrower sense, R, R¹, R², R³, m, n, p, u and Az preferably have the following meanings:

R and R¹ independently of another are each F, Cl, Br, C₁ -C₅ -alkyl, methoxy, ethoxy, methylthio, ethylthio, C₁ -C₃ -haloalkyl containing not more than 4 fluorine or chlorine atoms, or unsubstituted or substituted phenyl or phenoxy,

R² is hydrogen,

R³ is --(CH₂)_m --, --(CH₂ CH₂ O)_u --CH₂ CH₂ --, --CH₂ --CH═CH--CH₂ -- or --CH₂ --C.tbd.C--CH₂ --,

n, p and u are each 1, 2 or 3,

m is from 2 to 8, and

Az is 1,2,4-triazol-1-yl, pyrazol-1-yl or imidazol-1-yl;

salts of the compounds can also be used.

Herbicidal agents are obtained in particular when R³ is a divalent radical --(CH₂)_m --, where m is 2, 3 or 4.

Examples of salts of the azolylacetophenone oxime ethers of the formula (I) are the hydrochlorides, hydrobromides, sulfates, phosphates and p-toluenesulfonates.

A metal complex is, for example, an adduct of one equivalent of a zinc or copper salt, e.g. CuCl₂ or ZnCl₂, with two equivalents of a compound (I).

PREPARATION EXAMPLE

PAC 2,4-Dichloro-ω-[1,2,4-triazol-1-yl]-acetophenoneoxime O-[2-(4-chlorophenoxy)ethyl] ether, E and Z isomers

23 g (0.085 mole) of 2,4-dichloro-ω-[1,2,4-triazol-1-yl]-acetophenone oxime, 20 g of 2-[4-chlorophenoxy]-bromoethane, 7.1 g of powdered KOH and 5.8 g of triethylbenzylammonium chloride in 100 ml of toluene are stirred vigorously at 80°-100°C for 1 hour. The mixture is evaporated down, the residue is taken up in 250 ml of dichloromethane, the solution is washed with three times 100 ml of water, and the organic phase is dried with sodium sulfate and evaporated down. Chromatography over silica gel, using dichloromethane as eluant, gives 6 g of the Z isomer (active ingredient No. 23) and 4 g of the E isomer of 2,4-dichloro-ω-[1,2,4-triazol-1-yl]-acetophenone oxime O-[2-(4-chlorophenoxy)-ethyl] ether (active ingredient No. 24). The Z isomer is the first to be eluted.

The compounds listed in the Table below can be prepared in a similar manner. The configuration in which the oxime oxygen and the C aromatic ring are on the same side of the oxime double bond is designated E, while the corresponding, other isomer is designated Z.

Tri=1,2,4-triazol-1-yl, Pyr=pyrazol-1-yl, Im=imidazolyl, Ts=tosyl, Bu=butyl and Me=methyl.

Those compounds of the formula I which are shown in the Table below and for which melting points (mp.) or characteristics bands are given were prepared in a similar manner. Their structures were confirmed by elemental analysis. The compounds for which no physicochemical data are given can be obtained in the manner described for the compounds actually prepared; because of their similar constitution, they are expected to have actions similar to those of the compounds investigated in detail.

TABLE A
__________________________________________________________________________
Compounds of the formula I with R3 = (CH2)m:
##STR3##
No. Rn Rp1
R2 Az     Configuration
m  M.p. [°C.]
__________________________________________________________________________
1   H       H     H       Tri    E/Z mixture
2
2   H       H     H       Tri    E/Z mixture
4  oil
3   H       H     H       Tri    E/Z mixture
6
4   H       H     H       Tri    E/Z mixture
8
5   4-Cl    H     H       Tri    E/Z mixture
2  96-98
6   4-Br    H     H       Tri    E/Z mixture
2  89-90
7   4-OMe   H     H       Tri    E/Z mixture
2
8   4-CN    H     H       Tri    E/Z mixture
2
9   4-CF3
H     H       Tri    E/Z mixture
2
10  4-NO2
H     H       Tri    E/Z mixture
2
11  4-OC6 H5
H     H       Tri    E/Z mixture
2
12  2,4-Cl2
H     H       Tri.HNO 3
E/Z mixture
2  96
13  2,4-Cl2
H     H       Tri    Z      3  oil
14  2,4-Cl2
H     H       Tri    E      3  oil
15  2,4-Cl2
H     H       Tri    Z      4  oil
16  2,4-Cl2
H     H       Tri    E      4  oil
17  2,4-Cl2
H     H       Tri    Z      5  oil
18  2,4-Cl2
H     H       Tri    E      5  oil
19  2,4-Cl2
H     H       Tri    Z      6  oil
20  2,4-Cl2
H     H       Tri    E      6  oil
21  2,4-Cl2
H     H       Tri    E      8
22  2,4-Cl2
H     H       Tri    E      8
23  2,4-Cl2
4-Cl  H       Tri    Z      2  87-91
24  2,4-Cl2
4-Cl  H       Tri    E      2  58-61
25  2,4-Cl2
4-Cl  H       Tri.HNO3
E/Z mixture
2
26  2,4-Cl2
4-Cl  H       Tri.HNO3
E/Z mixture
2
27  2,4-Cl2
4-Cl  H       Tri.H2 SO4
E/Z mixture
2
28  2,4-Cl2
4-Cl  H       Tri.H3 PO4
E/Z mixture
2
29  2,4-Cl2
4-Cl  H       Tri.TsOH
E/Z mixture
2
30  2,4-Cl2
4-Cl  H       Tri.1/2 CuCl2
E/Z mixture
2
31  2,4-Cl2
4-Cl  H       Tri.1/2 ZnCl2
E/Z mixture
2
32  2,4-Cl2
4-Cl  CH3
Tri    E/Z mixture
2
33  2,4-Cl2
4-Cl  n-Bu    Tri    E/Z mixture
2
34  2,4-Cl2
4-Cl  CH2 C6 H5
Tri    E/Z mixture
2
35  2,4-Cl2
4-Cl  CH2 C(CH3)3
Tri    E/Z mixture
2
36  2,4-Cl2
4-Cl  H       Tri    Z      3  oil
37  2,4-Cl2
4-Cl  H       Tri    E      3  oil
38  2,4-Cl2
4-Cl  H       Tri    Z      4  65-71
39  2,4-Cl2
4-Cl  H       Tri    E      4  oil
40  2,4-Cl2
4-Cl  H       Tri    Z      5  oil
41  2,4-Cl2
4-Cl  H       Tri    E      5  59-62
42  2,4-Cl2
2,4-Cl2
H       Tri    Z      2   95-100
43  2,4-Cl2
2,4-Cl2
H       Tri    E      2  oil
44  2,4-Cl2
2,4-Cl2
CH3
Tri    E/Z mixture
2
45  2,4-Cl2
2,4-Cl2
n-Bu    Tri    E/Z mixture
2
46  2,4-Cl2
2,4-Cl2
CH2C6 H5
Tri    E/Z mixture
2
47  2,4-Cl2
2,4-Cl2
CH2C(CH3)
Tri    E/Z mixture
2
48  2,4-Cl2
2,4-Cl2
H       Tri.HNO3
E/Z mixture
2  132 (decomposition)
49  2,4-Cl2
2,4,6-Cl3
H       Tri.HCl
E/Z mixture
2
50  2,4-Cl2
2,4,6-Cl3
H       Tri.1/2 ZnCl2
E/Z mixture
2
51  2,4-Cl2
2,4,6-Cl3
H       Tri.1/2 CuCl2
E/Z mixture
2
52  2,4-Cl2
4-F   H       Tri    Z      2  66-70
53  2,4-Cl2
4-F   H       Tri    E      2  73-77
54  2,4-Cl2
4-CN  H       Tri    Z      2   96-100
55  2,4-Cl2
4-CN  H       Tri    E      2
56  2,4-Cl2
4-tert.-Bu
H       Tri.HNO3
E/Z mixture
2  117
57  2,4-Cl2
4-OMe H       Tri    Z      2  oil
58  2,4-Cl2
4-OMe H       Tri    E      2
59  2,4-Cl2
4-SMe H       Tri    E/Z mixture
2
60  2,4-Cl2
4-Br  H       Tri    E/Z mixture
2
61  2,4-Cl2
4-NO2
H       Tri    E/Z mixture
2
62  2,4-Cl2
3-Cl  H       Tri    Z      2  oil
63  2,4-Cl2
3-Cl  H       Tri    E      2  73-77
64  2,4-Cl2
3-CF3
H       Tri    Z      2  oil
65  2,4-Cl2
3-CF3
H       Tri    E      2  66-69
66  2,4-Cl2
4-Cl  CH2 HCCH2
Tri    E/Z mixture
2
67  2,4-Cl2
4-Cl  CH2 CClCCl2
Tri    E/Z mixture
2
68  2,4-Cl2
4-Cl  propargyl
Tri    E/Z mixture
2
69  2,4-Cl2 -3-CH3
4-Cl  H       Tri    E/Z mixture
2  oil
70  2,5-Cl2
4-Cl  H       Tri    Z      2  oil
71  2,5-Cl2
H     H       Tri    E      2  82-86
72  2,4-Cl2
H     H       Pyr    E/Z mixture
2
73  2,4-Cl2
H     H       Pyr    E/Z mixture
3
74  2,4-Cl2
H     H       Pyr    E/Z mixture
4
75  2,4-Cl2
H     H       Pyr    E/Z mixture
5
76  2,4-Cl2
4-Cl  H       Pyr    E/Z mixture
2
77  2,4-Cl2
4-F   H       Pyr    E/Z mixture
2
78  2,4-Cl2
4-CN  H       Pyr    E/Z mixture
2
79  2,4-Cl2
4-OMe H       Pyr    E/Z mixture
2
80  2,4-Cl2
4-Cl  CH3
Pyr    E/Z mixture
2
114 2,4-Cl2
2,4,6-Cl3
H       Tri    Z isomer
2  76-85
127 4-Cl    2,4,6-Cl3
H       Tri    Z isomer
2  114-116
128 H       4-Cl  H       Tri    Z isomer
2  79-83
129 H       4-Cl  H       Tri    Z isomer
3  59-64
130 H       4-Cl  H       Tri    Z isomer
4  59-62
131 H       3-Cl  H       Tri    Z isomer
2  73-75
132 H       3-CH3
H       Tri    Z isomer
2  54-56
133 H       H     H       Tri.1/2 CuCl2
E/Z mixture
4  wax-like
134 H       H     H       Tri.HCl
E/Z mixture
4  wax-like
135 H       H     H       Tri    E/Z mixture
4  oil
136 H       4-Cl  H       Tri.1/2 CuCl2.
E/Z mixture
4  wax-like
137 H       4-Cl  H       Tri.HCl
E/Z mixture
4  108-115
138 H       4-Cl  H       Tri    E/Z mixture
4  oil
139 H       4-Cl  H       Tri.1/2 CuCl2
E/Z mixture
2  wax-like
140 H       4-Cl  H       Tri.HCl
E/Z mixture
2  138-142
141 H       4-Cl  H       Tri    E/Z mixture
2  oil
142 H       3-Cl  H       Tri    E/Z mixture
2  oil
143 H       3-Cl  H       Tri.HCl
E/Z mixture
2  wax-like
144 H       3-Cl  H       Tri.1/2 CuCl2
E/Z mixture
2  wax-like
145 H       3-CH3
H       Tri    E/Z mixture
2  oil
146 H       3-CH3
H       Tri.HCl
E/Z mixture
2  wax-like
147 H       3-CH3
H       Tri.1/2 CuCl2
E/Z mixture
2  wax-like
148 4-CH3
4-Cl  H       Tri    Z isomer
2  110-112
149 4-CH3
4-Cl  H       Tri.HCl
Z isomer
2  164-167
150 4-CH3
3-Cl  H       Tri    Z isomer
2  86-91
151 4-CH3
3-Cl  H       Tri.HCl
Z isomer
2  oil
152 4-CH3
3-CH3
H       Tri    Z isomer
2  66-71
153 4-CH3
3-CH3
H       Tri.HCl
Z isomer
2  125-128
154 4-CH3
4-Cl  H       Tri    Z isomer
3  70-72
155 4-CH3
4-Cl  H       Tri.HCl
Z isomer
3  160-163
156 4-CH3
H     H       Tri    Z isomer
4  58-61
157 4-CH3
H     H       Tri.HCl
Z isomer
4  120-124
158 4-CH3
4-Cl  H       Tri    Z isomer
4  75-76
159 4-CH3
4-Cl  H       Tri.HCl
Z isomer
4  123-125
160 4-Cl    4-Cl  H       Tri    Z isomer
2  133-135
161 4-Cl    4-Cl  H       Tri.HCl
Z isomer
2  174-178
162 4-Cl    4-Cl  H       Tri    Z isomer
4  75-81
163 4-Cl    4-Cl  H       Tri.HCl
Z isomer
4  128-130
164 4-Cl    H     H       Tri    Z isomer
4  51-56
165 4-Cl    H     H       Tri.HCl
Z isomer
4  136
166 4-Cl    3-Cl  H       Tri    Z isomer
2  89-94
167 4-Cl    3-Cl  H       Tri.HCl
Z isomer
2  141-145
168 4-Cl    3-CH3
H       Tri    Z isomer
2  103-105
169 4-Cl    3-CH3
H       Tri.HCl
Z isomer
2  107-108
179 4-Cl    3-CF3
H       Tri           2  89-93
180 4-Cl    3,5-Cl2
H       Tri           2  88-94
181 4-CH3
3,5-Cl2
H       Tri           2  70-74
182 4-Cl    3-Cl  H       Tri           3  67-69
183 4-CH3
3-Cl  H       Tri           2  54-57
184 4-Cl    3-Cl  H       Im            2  119-123
185 4-Cl    3-Cl  H       Pyr           2  73-78
186 H       3-Cl  H       Im            2
187 H       3-Cl  H       Pyr           2  oil
188 4-Cl    3,4-Cl2
H       Tri    Z isomer
2  83
189 4-Cl    2,3-Cl2
H       Tri    Z isomer
2  103-106
190 4-Cl    3-OCH3
H       Tri    Z isomer
2  99
191 3,4-Cl2
3-Cl  H       Tri    Z isomer
2  84
192 4-F     3-Cl  H       Tri    Z isomer
2  71-74
193 3,4-Cl2
3-CH3
H       Tri    Z isomer
2  73-75
194 4-F     3-CH3
H       Tri    Z isomer
2  63-65
195 4-Cl    3-NO2
H       Tri    Z isomer
2  135-137
196 4-C6 H5
3-Cl  H       Tri    Z/E mixture
2  60-63
197 4-C6 H5
3-CH3
H       Tri    Z/E mixture
2  wax-like
198 4-Cl    2,4,5-Cl3
H       Tri    Z/E mixture
2  89
199 4-Cl    2,5-Cl2
H       Tri    Z/E mixture
2  124-126
200 4-OCH3
3-CF3
H       Tri    Z/E mixture
2  64-67
201 4-C6 H5
3-CF3
H       Tri    Z/E mixture
2  87-90
202 4-F     3-CF3
H       Tri    Z/E mixture
2  70-74
203 3,4-Cl2
3-CF3
H       Tri    Z/E mixture
2  90-94
204 4-OCH3
3-Cl  H       Tri    Z/E mixture
2  48-50
205 4-OCH3
3-CH3
H       Tri    Z/E mixture
2  oil
206 H       3-CH3
H       Tri    Z/E mixture
2
207 4-(CH3)2 CH
3-Cl  H       Tri    Z/E mixture
2
208 4-(CH3)2 CH
3-CH3
H       Tri    Z/E mixture
2
209 4-(CH3)2 CH
3,4-Cl2
H       Tri    Z/E mixture
2
210 4-(CH3)2 CH
2,3-Cl2
H       Tri    Z/E mixture
2
211 4-(CH3)2 C
3-CH3
H       Tri    Z/E mixture
2
212 4-(CH3)2 C
3-Cl  H       Tri    Z/E mixture
2
213 4-(CH3)3 C
3,4-Cl2
H       Tri    Z/E mixture
2
214 4-(CH3)3 C
2,3-Cl2
H       Tri    Z/E mixture
2
215 4-cycl.-C6 H11
3-CH3
H       Tri    Z/E mixture
2
216 4-cycl.-C6 H11
3-Cl  H       Tri    Z/E mixture
2
217 4-cycl.-C6 H11
3,4-Cl2
H       Tri    Z/E mixture
2
218 4-cycl.-C6 H11
2,3-Cl2
H       Tri    Z/E mixture
2
219 4-C6 H5
2,3-Cl2
H       Tri    Z/E mixture
2
220 4-C6 H5
2,3-Cl2
H       Tri    Z/E mixture
2
221 4-OCH3
2,3-Cl2
H       Tri    Z/E mixture
2
222 4-OCH3
3,4-Cl2
H       Tri    Z/E mixture
2
223 4-OC6 H5
3-Cl  H       Tri    Z/E mixture
2
224 4-OC6 H5
3-OCH3
H       Tri    Z/E mixture
2
225 4-OC6 H5
2,3-Cl2
H       Tri    Z/E mixture
2
226 4-OC6 H5
3,4-Cl2
H       Tri    Z/E mixture
2
237 4-NO2
3-Cl  H       Tri    Z/E mixture
2
238 4-NO2
3-CH3
H       Tri    Z/E mixture
2
239 4-NO2
3,4-Cl2
H       Tri    Z/E mixture
2
240 4-NO2
2,3-Cl2
H       Tri    Z/E mixture
2
241 2-Cl    3-Cl  H       Tri    Z/E mixture
2
242 2-Cl    3-CH3
H       Tri    Z/E mixture
2
243 2-Cl    2,3-Cl2
H       Tri    Z/E mixture
2
244 2-Cl    3,4-Cl2
H       Tri    Z/E mixture
2
245 3,5-Cl2
3-Cl  H       Tri    Z/E mixture
2
246 3,5-Cl2
3-CH3
H       Tri    Z/E mixture
2
247 4-Br    3-Cl  H       Tri    Z/E mixture
2
248 4-Br    3-CH3
H       Tri    Z/E mixture
2
249 H       3-Cl  CH3
Tri    Z/E mixture
2
250 H       3-CH3
CH3
Tri    Z/E mixture
2
251 H       3-Cl  CH2 CH3
Tri    Z/E mixture
2
252 H       3-CH3
CH2 CH3
Tri    Z/E mixture
2
253 H       3-Cl  CH2 CH2 CH3
Tri    Z/E mixture
2
254 H       3-CH3
CH2 CH2 CH3
Tri    Z/E mixture
2
255 4-F     3-F   H       Tri    Z/E mixture
2
256 H       2-F   H       Tri    Z      2
257 H       2-F   H       Tri    E      2
258 H       2-Cl  H       Tri    Z      2
259 H       2-Cl  H       Tri    E      2
260 4-CH3
2-F   H       Tri    Z      2
261 4-CH3
2-F   H       Tri    E      2
262 4-CH3
2-Cl  H       Tri    Z      2
263 4-CH3
2-Cl  H       Tri    E      2
264 4-cycl.C6 H11
2-F   H       Tri    Z      2
265 4-cycl.C6 H11
2-F   H       Tri    E      2  77-80
266 4-cycl.C6 H11
2-Cl  H       Tri    Z      2
267 4-cycl.C6 H11
2-Cl  H       Tri    E      2  wax-like
268 4-C6 H5
2-F   H       Tri    Z      2  111
269 4-C6 H5
2-F   H       Tri    E      2
270 4-C6 H5
2-Cl  H       Tri    Z      2  108
271 4-C6 H5
2-Cl  H       Tri    E      2
272 4-Cl    2-F   H       Tri    Z      2
273 4-Cl    2-F   H       Tri    E      2
274 4-Cl    2-Cl  H       Tri    Z      2
275 4-Cl    2-Cl  H       Tri    E      2
276 4-F     2-Cl  H       Tri    E/Z mixture
2  74-77
277 4-F     2-Cl  H       Tri    Z      2  81
278 4-F     2-Cl  H       Tri    E      2
279 4-F     2-F   H       Tri    Z      2  86
280 4-F     2-F   H       Tri    E      2
281 4-OCH3
2-F   H       Tri    Z      2  79-81
282 4-OCH3
2-F   H       Tri    E      2
283 4-OCH3
2-Cl  H       Tri    Z      2  71
284 4-OCH3
2-Cl  H       Tri    E      2
285 4-CN    2-F   H       Tri    Z      2
286 4-CN    2-F   H       Tri    E      2
287 H       2-CN  H       Tri    Z      2
288 H       2-CN  H       Tri    E      2
289 4-CH3
2-CN  H       Tri    Z      2
290 4-CH3
2-CN  H       Tri    E      2
291 4-Cl    2-CN  H       Tri    Z      2
292 4-Cl    2-CN  H       Tri    E      2
293 4-F     2-CN  H       Tri    Z      2
294 4-F     2-CN  H       Tri    E      2
295 H       2-CH3
H       Tri    Z      2
296 H       2-CH3
H       Tri    E      2
297 4-CH3
2-CH3
H       Tri    Z      2
298 4-CH3
2-CH3
H       Tri    E      2
299 4-Cl    2-CH3
H       Tri    Z      2
300 4-Cl    2-CH3
H       Tri    E      2
301 4-F     2-CH3
H       Tri    Z      2
302 4-F     2-CH3
H       Tri    E      2
303 H       2-OCH3
H       Tri    Z      2
304 H       2-OCH3
H       Tri    E      2
305 2-CH3
2-OCH3
H       Tri    Z      2
306 2-CH3
2-OCH3
H       Tri    E      2
307 2-Cl    2-OCH3
H       Tri    Z      2
308 2-Cl    2-OCH3
H       Tri    E      2
309 2-F     2-OCH3
H       Tri    Z      2
310 2-F     2-OCH3
H       Tri    E      2
311 3-Cl    2-Cl  H       Tri    Z      2
312 3-Cl    2-F   H       Tri    Z      2
313 3-Br    2-Cl  H       Tri    Z      2
314 3,4-Cl2
2-Cl  H       Tri    Z      2  98
315 3,4-Cl2
2-F   H       Tri    Z      2  103-105
316 3,5-Cl2
2-F   H       Tri    Z      2  117
317 3,5-Cl2
2-Cl  H       Tri    Z      2  108
318 2,5-Cl2
2-F   H       Tri.HNO3
Z      2  110
319 2,5-Cl2
2-Cl  H       Tri    Z      2  wax-like
320 2,4-Cl2
2-F   H       Tri    Z      2
321 2,4-Cl2
2-Cl  H       Tri    Z      2
322 2-Cl    2-F   H       Tri    Z      2
323 2-Cl    2-Cl  H       Tri    Z      2
324 H       2,6-Cl2
H       Tri    Z      2
325 4-CH3
2,6-Cl2
H       Tri    Z      2
326 4-Cl    2,6-Cl2
H       Tri    Z      2
327 4-F     2,6-Cl2
H       Tri    Z      2
328 2,5-Cl2
3-Cl  H       Tri    Z      2  oil
329 3-Br    3-Cl  H       Tri    Z      2  100-103
__________________________________________________________________________

TABLE B
______________________________________
Compounds of the formula I with R3 = (CH2 CH2 O)u
CH2 CH2
##STR4##
M.p.
No.  Rn Rp1
R2
Az   Configuration
m   [°C.]
______________________________________
81  2,4-Cl2
H        H   Tri  E/Z mixture
1
82  2,4-Cl2
H        H   Tri  E/Z mixture
2   oil
83  2,4-Cl2
H        H   Tri  E/Z mixture
3
84  2,4-Cl2
4-Cl     H   Tri  E/Z mixture
1
85  2,4-Cl2
4-Cl     H   Tri  E/Z mixture
2   oil
86  2,4-Cl2
4-Cl     H   Tri  E/Z mixture
3
87  2,4-Cl2
2,4-Cl2
H   Tri  E/Z mixture
1
88  2,4-Cl2
2,4-Cl2
H   Tri  E/Z mixture
2   oil
89  2,4-Cl2
2,4-Cl2
H   Tri  E/Z mixture
3
106  2,4-Cl2
2-Cl     H   Tri  E/Z mixture
2   oil
107  2,4-Cl2
3-Cl     H   Tri  E/Z mixture
2   oil
108  2,4-Cl2
4-OCH3
H   Tri  Z isomer 2   oil
109  2,4-Cl2
2,4,6-Cl3
H   Tri  Z isomer 2   oil
110  2,4-Cl2
2-Cl     H   Tri  E/Z mixture
1   wax-like
111  2,4-Cl2
4-OCH3
H   Tri  Z isomer 1   wax-like
112  2,4-Cl2
3-CH3
H   Tri  Z isomer 1   wax-like
113  2,4-Cl2
4-CH3
H   Tri  Z isomer 1   wax-like
116  4-Cl    2,4,6-Cl3
H   Tri  Z isomer 1   69-71
117  4-Cl    2-Cl     H   Tri  Z isomer 1   63-65
118  4-Cl    3-CH3
H   Tri  Z isomer 1   66-68
119  4-Cl    4-OCH3
H   Tri  Z isomer 1   71
120  4-Cl    4-CH3
H   Tri  Z isomer 1   79
121  4-Cl    H        H   Tri  Z isomer 2   oil
122  4-Cl    4-Cl     H   Tri  Z isomer 2   85-88
123  4-Cl    2-Cl     H   Tri  Z isomer 2   oil
124  4-Cl    3-Cl     H   Tri  Z isomer 2   oil
125  4-Cl    2,4-Cl2
H   Tri  Z isomer 2   48-53
126  4-Cl    4-OCH 3
H   Tri  Z isomer 2   oil
170  4-CH3
4-Cl     H   Tri  Z isomer 2   oil
171  H       4-Cl     H   Tri  Z isomer 2   oil
______________________________________

TABLE C
______________________________________
Compounds of the formula I with R3 =
(CH2)vCHCH(CH2)t
##STR5##
M.p.
No.  Rn Rp1
R2
Az   Configuration
v   t   [°C.]
______________________________________
90   2,4-Cl2
4        H   Tri  E/Z mixture
1   1   oil
91   2,4-Cl2
4-Cl     H   Tri  E/Z mixture
1   1   oil
92   2,4-Cl2
4-CH3
H   Tri  E/Z mixture
1   1
93   2,4-Cl2
4-OCH3
H   Tri  E/Z mixture
1   1
94   2,4-Cl2
2,4-Cl2
H   Tri  E/Z mixture
1   1   oil
95   2,4-Cl2
2,4,6-Cl2
H   Tri  E/Z mixture
1   1   oil
96   2,4-Cl2
4-Cl     H   Tri  E/Z mixture
2   2
97   2,4-Cl2
4-Cl     H   Tri  E/Z mixture
3   3
115  2,4-Cl2
2-Cl     H   Tri  E/Z mixture
1   1   84
______________________________________

TABLE D
__________________________________________________________________________
Compounds of the formula I with R3 = (CH2)vCC(CH2).sub
.t
##STR6##
No.
Rn
Rp1
R2
Az  Configuration
v  t   M.p. [°C.]
__________________________________________________________________________
98
2,4-Cl2
H     H  Tri E/Z mixture
1  1  oil
99
2,4-Cl2
4-Cl  H  Tri E/Z mixture
1  1  oil
100
2,4-Cl2
4-CH3
H  Tri E/Z mixture
1  1  oil
101
2,4-Cl2
4-OCH3
H  Tri E/Z mixture
1  1  oil
102
2,4-Cl2
2,4-Cl2
H  Tri E/Z mixture
1  1  oil
103
2,4-Cl2
3-CH3
H  Tri E/Z mixture
1  1  oil
104
2,4-Cl2
4-Cl  H  Tri E/Z mixture
2  2
105
2,4-Cl2
4-Cl  H  Tri E/Z mixture
3  3
172
2,4-Cl2
4-F   H  Tri Z isomer
1  1  oil
173
2,4-Cl2
3-Cl  H  Tri Z isomer
1  1  oil
174
4-Cl H     H  Tri Z isomer
1  1  70-75
175
4-Cl 4-Cl  H  Tri Z isomer
1  1  81-85
176
4-Cl 4-F   H  Tri Z isomer
1  1  70-75
177
4-Cl 3-Cl  H  Tri Z isomer
1  1  80-85
178
4-Cl 4-OCH3
H  Tri Z isomer
1  1  oil
__________________________________________________________________________

______________________________________
Characteristic NMR data (1 H-NMR):
No.   δ in ppm, solvent CDCl3
______________________________________
13    4.05 "t" 2H; 4.45 "t" 2H; 5.39 s 2H, 7.72 s 1H;
7.98 s 1H
14    3.90 "t" 2H; 4.25 "t" 2H; 5.10 s 2H; 7.82 s 1H;
7.90 s 1H
15    4.00 "t" 2H; 4.35 "t" 2H; 5.40 s 2H; 7.80 s 1H;
8.07 s 1H
16    3.90 "t" 2H; 4.20 "t" 2H; 5.20 s 2H; 7.90 s 1H;
8.00 s 1H
17    4.00 "t" 2H; 4.30 "t" 2H; 5.44 s 2H; 7.82 s 1H;
8.10 s 1H
18    3.90 "t" 2H; 4.20 "t" 2H; 5.20 s 2H; 7.93 s 1H;
8.04 s 1H
36    4.03 "t" 2H; 4.43 "t" 2H; 5.44 s 2H; 7.80 s 1H;
8.07 s 1H
37    3.90 "t" 2H; 4.27 "t" 2H; 5.20 s 2H; 7.90 s 1H;
8.00 s 1H
39    3.78 "t" 2H; 4.08 "t"  2H; 5.05 s 2H; 7.70 s 1H;
7.85 s 1H
40    3.38 "t" 2H; 4.20 "t" 2H; 5.35 s 2H; 7.70 s 1H;
7.98 s 1H
43    4.22 "t" 2H; 4.48 "t" 2H; 5.23 s 2H; 7.98 s 1H;
8.03 s 1H
57    4.25 "t" 2H; 4.60 "t" 2H; 5.47 s 2H; 7.80 s 1H;
8.17 s 1H
62    4.27 "t" 2H; 4.60 "t" 2H; 5.48 s 2H; 7.80 s 1H;
8.15 s 1H
64    4.43 "t" 2H; 4.63 "t" 2H; 5.45 s 2H; 7.80 s 1H;
8.13 s 1H
69    2.41 3H; 4.22 "t" 2H; 4.58 "t" 2H; 5.41 s 2H;
7.78 s 1H; 8.11 s 1H
70    4.22 "t" 2H; 4.59 "t" 2H; 5.42 s 2H; 7.81 s 1H;
8.14 s 1H
98    4.78 s 4H; 5.22 s 2H; 7.93 s 1H; 8.03 s 1H
100   2.28 s 3H; 4.70 m 3H; 5.20 s 2H; 7.90 s 1H;
8.00 s 1H
101   3.72 s 3H; 4.70 s 2H; 4.87 s 2H; 5.44 s 2H;
7.80 s 1H; 8.11 s 1H
102   4.70 m 4H; 5.20 s and 5.50 s 2H; 7.80 s and 7.94 s 1H;
8.01 s and 8.10 s 1H
103   2.31 s 3H; 4.72 s 2H; 4.87 s 2H; 5.44 s 2H; 7.80 s 1H;
8.10 s 1H
112   3.75 m 4H; 4.15 m 2H; 4.35 m 2H, 5.53 s 2H; 7.83 s 1H;
8.50 s 1H
113   3.75 m 4H; 4.15 m 2H; 4.38 m 2H; 5.53 s 2H; 7.85 s 1H;
8.50 s 1H
121   3.75 m 8H; 4.15 m 2H; 4.40 m 2H; 5.35 s 2H; 7.88 s 1H;
8.38 s 1H
123   3.80 m 8H; 4.15 m 2H; 4.45 m 2H; 5.38 s 2H; 7.88 s 1H;
8.38 s 1H
124   3.70 m 8H; 4.15 m 2H; 4.30 m 2H; 5.45 s 2H; 7.78 s 1H;
8.45 s 1H
126   3.80 m 8H; 4.10 m 2H; 4.40 m 2H; 5.60 s 2H; 8.05 s 1H;
8.70 s 1H
170   3.70 m 8H; 4.00 m 2H; 4.35 m 2H; 5.30 s 2H; 7.75 s 1H;
8.43 s 1H
171   3.80 m 8H; 4.10 m 2H; 4.45 m 2H; 5.40 s 2H; 7.90 s 1H;
8.40 s 1H
172   4.60 "t" 2H; 4.80 "t" 2H; 5.40 s 2H;, 7.70 s 1H;
7.98 s 1H
173   4.65 "t" 2H; 4.85 "t" 2H; 5.40 s 2H;, 7.70 s 1H;
8.00 s 1H
141   4.20 "t" 2H; 4.45 "t" 2H; 5.21 s 2H; 7.91 s 1H;
8.13 s 1H
142   4.20 "t" 2H; 4.42 "t" 2H; 5.19 s 2H; 7.90 s 1H;
8.02 s 1H
145   4.20 "t" 2H; 4.45 "t" 2H; 5.20 s 2H; 7.90 s 1H;
8.02 s 1H
135   1.8 m 4H; 3.90 "t" 2H; 4.18 "t" 2H; 5.18 s 2H;
7.89 s 1H; 8.00 s 1H
106   3.7 m 8H; 4.2 m 4H; 5.55 s 2H; 7.87 s 1H; 8.52 s 1 H
107   3.7 m 8H; 4.2 m 4H; 5.57 s 2H; 7.85 s 1H; 8.50 s 1H
108   3.7 m 8H; 4.0 m 2H;; 4.45 m 2H; 5.55 s 2H; 7.88 s 1H;
8.5 s 1H
109   3.7 m 8H; 4.25 m 4H; 5.55 s 2H; 7.85 s 1H; 8.50 s 1H
110   3.8 m 4H; 4.20 m 4H; 5.45 s 2H; 7.75 s 1H; 8.40 s 1H
111   3.75 m 4H; 4.05 m 2H; 4.35 m 2H; 5.53 s 2H; 7.83 s 1H;
8.50 s 1H
178   4.65 "t" 2H; 4.85 "t" 2H; 5.30 s 2H; 7.80 s 1H;
8.10 s 1H
186   4.30 "t" 2H; 4.65 "t" 2H; 5.22 s 2H; 6.8-7.7 m; 12H
187   4.20 m 2H; 4.55 m 2H; 5.35 s 2H; 6.08 t 1H;
6.6-7.8 m; 1H
197   4.25 "t" 2H; 4.60 "t" 2H; 5.42 s 2H; 7.88 s 1H;
8.28 s 1H
205   4.25 "t" 2H; 4.55 "t" 2H; 5.32 s 2H; 7.90 s 1H;
8.28 s 1H.
______________________________________
s = singlet
"t" = pseudo-triplet
m = multiplet

The novel compounds may influence virtually all development stages of a plant in different ways, and are therefore employed as growth regulators or herbicides.

USE EXAMPLES

I. To determine the growth-regulating properties of the candidate compounds, soil provided with sufficient nutrients was filled into plastic pots about 12.5 cm in diameter and summer rape plants were growth therein.

The compounds were sprayed onto the plants (post-emergence treatment). The growth-regulating action observed was confirmed at the end of the experiment by height measurements. The values obtained were compared with those for untreated plants.

The compounds used for comparison purposes were active ingredients A and B having the structural formulae given below.

Not only was growth height reduced--the leaves also took on a more intense color. The increased chlorophyll content is indicative of a higher rate of photosynthesis, making for bigger yields.

Comparative agents: ##STR7##

The results show that active ingredients 13, 15, 52, 57, 62, 64, 101, 103, 116, 117, 119, 121, 122 and 123, applied for example at a rate of 1.5 or 6 mg per vessel, reduced growth height to a greater extent (e.g., 68% or 57%) than active ingredients A and B (e.g., 94% and 83%).

II. In the same manner as described under I, summer wheat of the Kalibri variety (Table 1) and summer barley of the Aramir variety (Table 2) were treated postemergence. The following results were obtained:

TABLE 1
______________________________________
No. of chemical
mg of active ingre-
Relative growth
example     dient per vessel
height
______________________________________
--          --              100
A           1.5             99.2
6               84.8
B           1.5             99.5
6               94.0
131         1.5             73.2
6               71.6
142         1.5             79.2
6               73.2
255         1.5             77.4
6               71.9
276         1.5             70.1
6               70.1
______________________________________

TABLE 2
______________________________________
No. of chemical
mg of active ingre-
Relative growth
example     dient per vessel
height
______________________________________
--          --              100
A           1.5             93.4
6               93.4
B           1.5             95.3
6               95.3
131         1.5             86.8
6               77.2
142         1.5             92.9
6               92.9
255         1.5             87.9
6               84.3
276         1.5             84.3
6               84.3
______________________________________

The herbicidal action of compounds of the formula I is demonstrated in greenhouse experiments.

The vessels employed were plastic flowerpots having a volume of 300 cm³, and which were filled with a sandy loam containing about 1.5% humus. The seeds of the test plants were sown shallow, and separately, according to species. For the preemergence treatment, the active ingredients were applied to the surface of the soil immediately after the seeds had been sown. The compounds were emulsified or suspended in water as vehicle, and sprayed through finely distributing nozzles. The application rates were 3.0 and 1.0 kg of active ingredient per hectare. After the agents had been applied, the vessels were lightly sprinkler-irrigated to induce germination an growth. Transparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensured uniform germination of the plants, insofar as this was not impaired by the active ingredients.

For the postemergence treatment, the plants were first grown in the vessels to a height of from 3 to 15 cm, depending on growth form, before being treated. The soybean and rice plants were grown in a peat-enriched substrate. For this treatment, either plants which had been sown directly in the pots and grown there were selected, or plants which had been grown from seedlings and were transplanted to the pots a few days before treatment. The application rate for postemergence treatment was for example 1.0 kg of active ingredient per hectare.

The pots were set up in the greenhouse--species from warmer areas at from 20° to 30°C, and species from moderate climates at 15° to 25°C The experiments were run for 2 to 4 weeks. During this period, the plants were tended and their reactions to the various treatments assessed. The scale used for assessment was 0 to 100, 0 denoting no damage or normal emergence, and 100 denoting nonemergence or complete destruction of at least the visible plant parts.

The plants used in the experiments were Amaranthus spp., Centaurea cyanus, Chenopodium album, Echinochloa, crus-galli, Galeopsis spp., Gaalium aparine, Glycine max., Ipomoea spp., Lamium amplexicaule, Lolium multiflorum, Lycopersicon lycopersicum, Mercurialis annua, Stellaria media, Triticum aestivum, Viola spp., and Zea mays.

At an application rate of 3.0 kg/ha, compounds nos. 131, 153, 166 and 192 had a considerable herbicidal action on broadleaved and grassy plants (postemergence application).

Compound no. 166, applied postemergence at a rate of 0.5 kg/ha, and compounds nos. 133, 142, 143, 150 and 167 at 1.0 kg/ha are suitable for selectively combatting unwanted plants in crops. Compounds nos. 166 and 204 combatted broadleaved weeds at a rate of 2.0 kg/ha.

TABLE 3
__________________________________________________________________________
Selective control of broadleaved unwanted plants
in wheat on postemergence application in the
greenhouse
Com-    Test plants and % damage
pound   Triticum*
Galeopsis
Lamium
Mercurialis
Stellaria
no. kg/ha
aestivum
spp. ampl. annua media
__________________________________________________________________________
166 2.0 0      100  100   100   100
204 2.0 0      100  100    98   100
__________________________________________________________________________
"Vuka" variety

Claims

1. A process for combatting the growth of unwanted plants, wherein the plants or the soil in which they are located are treated with a herbicidally effective amount of an azolylacetophenone ether of the formula I ##STR8## where R and R₁ independently of one another are each hydrogen, halogen, alkyl of 1-5 carbons, cyclohexyl, alkoxy of 1-2 carbons, alkylthio of 1-2 carbons, alkylsulfonyl of 1-4 carbons, haloalkyl of 1-4 carbons and 1-5 halogen atoms, nitro, cyano, unsubstituted or substituted phenyl or unsubstituted or substituted phenoxy, R² is hydrogen or alkyl of 1-4 carbons, R³ is a divalent radical of the formula --(CH₂)_m --, --(CH₂ --CH₂ O--)_u CH₂ CH₂ --, --(CH₂)CH═CH--(CH₂)-- or --(CH₂)C.tbd.C--(CH₂)--, n, p or u independently of one another are each 1, 2 or 3, m is an integer from 2 to 10 and Az is 1,2,4-triazol-1-yl, pyrazol-1-yl or imidazol-1-yl, or their salts or metal complexes.

2. A process according to claim 1, wherein R and R¹ in formula I independently of one another are fluorine, chlorine, bromine, C₁ -C₅ -alkyl, methoxy, ethoxy, methylthio, ethylthio, C₁ -C₃ -haloalkyl of a maximum of 5 fluorine or chlorine atoms, substituted or unsubstituted phenyl or substituted or unsubstituted phenoxy, R² is hydrogen, R³ is --(CH₂)_m --, n and p are each 1, m is 2, 3 or 4, and Az is 1,2,4-triazol-1-yl.

3. A process according to claim 2, with the proviso that R³ is --(CH₂)_m -- and m is 2.

4. A process for combatting the growth of unwanted plants, wherein the plants or the soil in which they are located are treated with 0,5 to 3 kg/ha of an azolylacetophenone ether herbicide of the formula ##STR9## where R and R₁ independently of one another are each hydrogen, halogen, alkyl of 1-5 carbons, cyclohexyl, alkoxy of 1-2 carbons, alkylthio of 1-2 carbons, alkylsulfonyl of 1-4 carbons, haloalkyl of 1-4 carbons and 1-5 halogen atoms, nitro, cyano, unsubstituted or substituted phenyl or unsubstituted or substituted phenoxy, R² is hydrogen or alkyl of 1-4 carbons, R³ is a divalent radical of the formula --(CH₂)_m --, --(CH₂ --CH₂ O--)_u CH₂ CH₂ --, --(CH₂)CH═CH--(CH₂)-- or --(CH₂)C.tbd.C--(CH₂)--, n, p or u independently of one another are each 1, 2 or 3, m is an integer from 2 to 10 and Az is 1,2,4-triazol-1-yl, pyrazol-1-yl or imidazol-1-yl, or their salts or metal complexes.